1. Field of the Invention
This invention concerns the preparation of ditertiary organic disulfides from ditertiary organic sulfides.
2. Description of the Prior Art
Generally, organic disulfides and polysulfides are produced from thiol compounds. Typical examples of such methods of producing organic polysulfides or disulfides are shown in the following patents: U.S. Pat. Nos. 2,503,644; 3,022,351; 3,340,324; 3,387,039; 3,397,244; 3,586,723; and 3,755,461. Also, J. Org. Chem. 28, 3246-3247 (1963) discloses the production of organic disulfides by the oxidation of a thiol with dimethyl sulfoxide.
In accordance with the present invention, ditertiary organic disulfides are produced from ditertiary organic sulfides.
Accordingly, it is an object of this invention to provide a method for preparing ditertiary organic disulfides from ditertiary organic sulfides.
A further object of this invention is to provide a method of preparing ditertiary alkyl disulfides from the corresponding ditertiary alkyl sulfides.
Other aspects, objects, as well as the advantages of the invention will be apparent from this disclosure and the appended claims.
According to this invention ditertiary organic disulfides can be prepared by contacting under suitable reaction conditions at least one ditertiary organic sulfide and at least one hydrocarbyl sulfoxide in the presence of a reaction promoting amount of at least one protonic acid.
The term ditertiary organic sulfide denotes those sulfides having the formula ##STR1## wherein each R may be the same or different radical selected from the group consisting of hydrocarbyl radicals and substituted hydrocarbyl radicals. The term substituted hydrocarbyl radicals denotes those hydrocarbyl radicals that contain suitable substituents containing elements other than carbon and hydrogen. Examples of suitable substituents include ##STR2## and halogens, where R" is again a hydrocarbyl radical having from 1 to 12 carbon atoms. The preferred ditertiary organic sulfides are those in which each R is individually selected from hydrocarbyl radicals having from 1 to 12 carbon atoms. Examples of such ditertiary organic sulfides include ditertiary butyl sulfide, ditertiary amyl sulfide, ditertiary octyl sulfide, ditertiary tetradecyl sulfide, (di(1,1-diethyl ethyl)sulfide, di(1,1-dimethyl-1-phenyl methyl)sulfide, tertiary butyl-tertiary octyl sulfide, tertiary butyl-1,1-dimethyl-1-phenyl methyl sulfide, and the like and mixtures of any two or more thereof. Especially preferred ditertiary organic sulfide reactants are those in which each R is an alkyl radical having from 1 to 12 carbon atoms.
When the two tertiary groups in a ditertiary organic sulfide are not the same there is the possibility to obtain three different disulfide products, one containing both tertiary groups, one in which both organic substituents are identical to one of the tertiary groups in the reactant, and another in which both organic substituents are identical to the other of the tertiary groups in the reactant.
The hydrocarbyl sulfoxides suitable for use in this invention are those of the formula ##STR3## wherein each R' may be the same or different alkyl radical having from 1 to 12 carbon atoms or wherein the two such R' alkyl groups are combined by a bond to form a cyclic ring containing at least 4 carbons in the cyclic ring in addition to the sulfur atom. Examples of such hydrocarbyl sulfoxides include dimethyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, didodecyl sulfoxide, tetramethylene sulfoxide, and mixtures of any two or more thereof.
Any suitable protonic acid can be used to promote the reaction herein disclosed. Examples of protonic acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, nitric acid, acetic acid, propionic acid, trichloroacetic acid, chlorosulfuric acid, phthalic acid, benzenesulfonic acid, and the like and mixtures of any two or more thereof. Especially preferred protonic acids are hydrochloric, hydrobromic, and hydroiodic acids.
The employment of a small amount of at least one suitable Lewis acid in conjunction with the protonic acid can increase the rate of the reaction. Suitable Lewis acids include, for example, lead chloride, zinc chloride, aluminum chloride, tin tetrachloride, boron trifluoride, magnesium bromide, lead bromide, and the like and mixtures of any two or more thereof.
Any suitable amounts of ditertiary organic sulfide and hydrocarbyl sulfoxide can be reacted. Generally, however, the molar ratio of hydrocarbyl sulfoxide to ditertiary organic sulfide is in the range of about 20/1 to about 1/20, preferably in the range of about 5/1 to about 2/1.
Although it is not necessary, it is preferred that the contacting of ditertiary organic sulfide and hydrocarbyl sulfoxide be conducted in the presence of a diluent. Suitable diluents include any organic liquid that is inert under the reaction conditions. Examples of suitable diluents include monohydric alcohols, for example, benzol, methanol, ethanol, butanol, and the like; ethers of the type R" -- 0 -- R'" where R" and R'" may be the same or different alkyl or aryl radicals, for example, diethyl ether, dipropyl ether, di-n-butyl ether, diphenyl ether, and the like, hydrocarbons, for example, benzene, toluene, heptane, hexane, and the like, or mixtures of any two or more inert diluents such as those set forth. The preferred diluents are saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms. Any suitable amount of diluent can be employed. Generally the number of moles of diluent is no greater than about 10 times the sum of the moles of ditertiary organic sulfide and hydrocarbyl sulfoxide and no less than about 0.01 of that sum. Preferably the number of moles of diluent is no greater than about 5 times the sum of the moles of ditertiary organic sulfide and alkyl sulfoxide and no less than about 0.1 of that sum.
The protonic acid can be employed in any amount that promotes the production of ditertiary organic disulfide. Generally the ratio of the moles of protonic acid to the sum of the moles of the hydrocarbyl sulfoxide and ditertiary organic sulfide is in the range of about 0.0001/1 to about 0.01/1, preferably in the range of about 0.001/1 to about 0.003/1.
Lewis acid, when employed, is employed in any amount that increases the rate of the reaction. Generally the ratio of the moles of Lewis acid to the sum of the moles of the hydrocarbyl sulfoxide and ditertiary organic sulfide will be in the range of about 0.001/1 to about 0.1/1, preferably in the range of about 0.005/1 to about 0.05/1.
Any suitable temperature conditions can be employed in the present invention. Generally the temperature is in the range of about 40.degree. C. to about 250.degree. C., preferably in the range of about 50.degree. C. to about 150.degree. C. When higher temperatures are used the yield of disulfide is reduced by the formation of increasing amounts of higher organic polysulfides, i.e., trisulfides and tetrasulfides.
Any suitable pressure conditions can be employed. It is preferred to conduct the reaction at atmospheric pressure. To limit the possibility of undesired side reactions it is also preferred to conduct the reaction under an inert atmosphere.
The following examples are to be construed as merely illustrative, and not unduly limitative of the remainder of the specification and claims.